Nesta dissertação, estudou-se um modelo tipo gás de rede em três dimensões para simular sistemas líquidos macroscópicos. Aplicou-se o modelo para o estudo das energias e forças envolvidas durante o processo de formação e ruptura de pontes líquidas entre duas placas planas. Esse estudo foi motivado por processos fisiológicos que acontecem no interior dos pulmões dos mamíferos. Além disso, foi feito um estudo das propriedades termodinâmicas do modelo. Com relação a aplicação fisiológica, observou-se que, no processo da formação da ponte líquida, a energia livre da ponte líquida é menor que a energia livre da gota, para diferentes sistemas líquidos. Com este resultado, fez a hipótese de que parte dessa energia é dissipada na forma de energia acústica. A emissão do som também deve ocorrer na ruptura da ponte líquida. Comparando a energia livre no processo de formação e ruptura da ponte líquida observou-se uma curva de histerese. Também foi verificado que para sistemas pequenos, a ponte líquida no modelo computacional se forma antes da previsão analítica. Para a análise termodinâmica, o modelo foi simplificado removendo as placas planas. Foi estudado o caso mais simples desse modelo que continha apenas duas partículas de líquido. Neste caso, calculou-se o calor específico e a energia interna numericamente, e esses resultados foram comparados com cálculos analíticos, validando o modelo numérico. Posteriormente, realizou-se um estudo da transição de fase desse sistema. Em seguida, a energia livre e a força da ponte líquida sobre as placas foram estudadas para diferentes temperaturas utilizando duas metodologias. Na primeira metodologia a entropia foi desprezada, na segunda metodologia, foi utilizando o método ``Overlapping Distribution\'\' que considera a entropia do sistema. Foi concluído que a entropia tem um efeito muito pequeno nas condições estudadas. O modelo é viável para a modelagem de fluidos a nível macroscópico e que portanto pode ser utilizado para quantificar não só as forças internas de estruturas pulmonares como também avaliar as energias liberadas após o processo de ruptura ou formação dessas pontes. / This work studied a three dimension lattice gas model to simulate macroscopic liquid systems. We used the model to study the energy and the forces involved during the process of liquid bridge formation and rupture between two parallel planes. The motivarion of this study was a physiological processes which occur inside the mammals lungs. Furthermore, a study was made to elucidate thermodynamic properties of the model. Concerning to physiological application, it was observed that the free energy of liquid bridge is smaller than the free energy of the droplet, for different liquid systems. With this observation, was proposed that this energy is dissipated as an acoustic energy. This sound should also exist in the rupture of liquid bridge. Comparing the free energy of liquid bridge in the formation and rupture process was observed a hysteresis curve. It was also found an effect of finite size in the formation of small size of the liquid bridge. In the numerical model, the liquid bridge is always formed earlier than expected from the analytical model. In the thermodynamic study, the model was simplified removing both parallel planes. First, the simplest case of this model was studied, only two liquid particles in a large gas lattice. In this case, the specific heat and internal energy was numerically studied and the results was compared with analytical calculation. Subsequently, we carried out a study of the phase transition of this system. Then, the free energy and the force generated between two parallel planes due the presence of the liquid bridge. This studied was performed using two different temperatures and two distinct methods. In the first method the entropy was neglected, and in the second method not. The second method was the ``Overlapping Distribution\'\'. It was concluded that the entropy has a very small effect in the studied conditions. The model is viable for modeling fluids at macroscopic level and therefore can be used to quantify not only the internal forces of the lung structures, but evaluate the energies released after the rupture process of the formation of these bridges.

Interfacial adhesion and friction are significant factors in determining the reliability of small-scale mechanical devices such as with MEMS and the computer head/disk interface (HDI). As the interface spacing becomes smaller, operational failure via stiction has become a growing concern in these systems. Fundamentally, interface failure is related to mechanical instability of the interface caused by capillary effects. When liquid is present in a small-scale interface, large concave meniscus curvatures often develop at the liquid-vapor interface, leading to negative pressures in the liquid film and large tensile forces on the surfaces. When the elastic restoring force cannot balance the capillary force, the interface will lose its stability and collapse into intimate contact (jump-on). In addition, when the elastic bodies are then pulled away from contact, separation may occur suddenly and is related to another form of instability (jump-off). The jump-on and jump-off behaviors determine the strength of interfacial adhesion. In this study, the interaction between two elastic bodies coupled via a small liquid bridge was investigated. Geometries of two half-spaces and two sphere contact were considered. Stable equilibrium configurations were determined, and the mechanical stability of the interface was examined. Jump-on and jump-off conditions were given out. Then the theory was applied to study the approach and detachment processes of two elastic spheres in the presence of a liquid bridge. Critical values of the control variables at jump-on and jump-off were found. The pull-off force was calculated as a measure of interfacial adhesion. The results provide insight on some experimental data in the literature.

<p><b>In this thesis the fabrication and analytical evaluation of two new electrospray emitters utilized for mass spectrometry analysis is presented. The emitters are based on a new concept, where the spray orifice can be varied in size. The thesis is based on two papers.</b></p><p>All present-day nanoelectrospray emitters have fixed dimensions. The range of the applicable flow rate for such an emitter is therefore rather limited and exchange of emitters may be necessary from one experiment to another. Optimization of the signal of the analyte ions is also limited to adjustments of the applied voltage or the distance between the emitter and the mass spectrometer inlet. Furthermore, clogging can occur in emitters with fixed dimensions of narrow orifice sizes. In this thesis, electrospray emitters with a variable size of the spray orifice are proposed. An open gap between two thin substrates is filled with sample solution via a liquid bridge from a capillary. Electrospray is generated at the end point of the gap, which can be varied in width.</p><p>In Paper I, electrospray emitters fabricated in polyethylene terephthalate have been evaluated. Triangular tips are manually cut from the polymer film. The tips are mounted to form a gap between the edges of the tips. The gap wall surfaces are subjected to a hydrophilic surface treatment to increase the wetting of the gap walls.</p><p>In Paper II, silicon electrospray chips with high precision are fabricated and evaluated. A thin beam, elevated from the bulk silicon chip is fabricated by means of deep reactive ion etching. The top surfaces of the beams of two chips act as a sample conduit when mounted in the electrospray setup. An anisotropic etching step with KOH of the intersecting <100> crystal planes results in a very sharp spray point. The emitters were given a hydrophobic surface treatment except for the hydrophilic gap walls.</p><p>For both emitter designs, the gap width has been adjusted during the experiments without any interruption of the electrospray. For a continuously applied peptide mixture, a shift towards higher charge states and increased signal to noise ratios could be observed when decreasing the gap width. The limit of detection has been investigated and the silicon chips have been interfaced with capillary electrophoresis.</p>

Nesta dissertação, estudou-se um modelo tipo gás de rede em três dimensões para simular sistemas líquidos macroscópicos. Aplicou-se o modelo para o estudo das energias e forças envolvidas durante o processo de formação e ruptura de pontes líquidas entre duas placas planas. Esse estudo foi motivado por processos fisiológicos que acontecem no interior dos pulmões dos mamíferos. Além disso, foi feito um estudo das propriedades termodinâmicas do modelo. Com relação a aplicação fisiológica, observou-se que, no processo da formação da ponte líquida, a energia livre da ponte líquida é menor que a energia livre da gota, para diferentes sistemas líquidos. Com este resultado, fez a hipótese de que parte dessa energia é dissipada na forma de energia acústica. A emissão do som também deve ocorrer na ruptura da ponte líquida. Comparando a energia livre no processo de formação e ruptura da ponte líquida observou-se uma curva de histerese. Também foi verificado que para sistemas pequenos, a ponte líquida no modelo computacional se forma antes da previsão analítica. Para a análise termodinâmica, o modelo foi simplificado removendo as placas planas. Foi estudado o caso mais simples desse modelo que continha apenas duas partículas de líquido. Neste caso, calculou-se o calor específico e a energia interna numericamente, e esses resultados foram comparados com cálculos analíticos, validando o modelo numérico. Posteriormente, realizou-se um estudo da transição de fase desse sistema. Em seguida, a energia livre e a força da ponte líquida sobre as placas foram estudadas para diferentes temperaturas utilizando duas metodologias. Na primeira metodologia a entropia foi desprezada, na segunda metodologia, foi utilizando o método ``Overlapping Distribution\'\' que considera a entropia do sistema. Foi concluído que a entropia tem um efeito muito pequeno nas condições estudadas. O modelo é viável para a modelagem de fluidos a nível macroscópico e que portanto pode ser utilizado para quantificar não só as forças internas de estruturas pulmonares como também avaliar as energias liberadas após o processo de ruptura ou formação dessas pontes. / This work studied a three dimension lattice gas model to simulate macroscopic liquid systems. We used the model to study the energy and the forces involved during the process of liquid bridge formation and rupture between two parallel planes. The motivarion of this study was a physiological processes which occur inside the mammals lungs. Furthermore, a study was made to elucidate thermodynamic properties of the model. Concerning to physiological application, it was observed that the free energy of liquid bridge is smaller than the free energy of the droplet, for different liquid systems. With this observation, was proposed that this energy is dissipated as an acoustic energy. This sound should also exist in the rupture of liquid bridge. Comparing the free energy of liquid bridge in the formation and rupture process was observed a hysteresis curve. It was also found an effect of finite size in the formation of small size of the liquid bridge. In the numerical model, the liquid bridge is always formed earlier than expected from the analytical model. In the thermodynamic study, the model was simplified removing both parallel planes. First, the simplest case of this model was studied, only two liquid particles in a large gas lattice. In this case, the specific heat and internal energy was numerically studied and the results was compared with analytical calculation. Subsequently, we carried out a study of the phase transition of this system. Then, the free energy and the force generated between two parallel planes due the presence of the liquid bridge. This studied was performed using two different temperatures and two distinct methods. In the first method the entropy was neglected, and in the second method not. The second method was the ``Overlapping Distribution\'\'. It was concluded that the entropy has a very small effect in the studied conditions. The model is viable for modeling fluids at macroscopic level and therefore can be used to quantify not only the internal forces of the lung structures, but evaluate the energies released after the rupture process of the formation of these bridges.

In this thesis the fabrication and analytical evaluation of two new electrospray emitters utilized for mass spectrometry analysis is presented. The emitters are based on a new concept, where the spray orifice can be varied in size. The thesis is based on two papers. All present-day nanoelectrospray emitters have fixed dimensions. The range of the applicable flow rate for such an emitter is therefore rather limited and exchange of emitters may be necessary from one experiment to another. Optimization of the signal of the analyte ions is also limited to adjustments of the applied voltage or the distance between the emitter and the mass spectrometer inlet. Furthermore, clogging can occur in emitters with fixed dimensions of narrow orifice sizes. In this thesis, electrospray emitters with a variable size of the spray orifice are proposed. An open gap between two thin substrates is filled with sample solution via a liquid bridge from a capillary. Electrospray is generated at the end point of the gap, which can be varied in width. In Paper I, electrospray emitters fabricated in polyethylene terephthalate have been evaluated. Triangular tips are manually cut from the polymer film. The tips are mounted to form a gap between the edges of the tips. The gap wall surfaces are subjected to a hydrophilic surface treatment to increase the wetting of the gap walls. In Paper II, silicon electrospray chips with high precision are fabricated and evaluated. A thin beam, elevated from the bulk silicon chip is fabricated by means of deep reactive ion etching. The top surfaces of the beams of two chips act as a sample conduit when mounted in the electrospray setup. An anisotropic etching step with KOH of the intersecting &lt;100&gt; crystal planes results in a very sharp spray point. The emitters were given a hydrophobic surface treatment except for the hydrophilic gap walls. For both emitter designs, the gap width has been adjusted during the experiments without any interruption of the electrospray. For a continuously applied peptide mixture, a shift towards higher charge states and increased signal to noise ratios could be observed when decreasing the gap width. The limit of detection has been investigated and the silicon chips have been interfaced with capillary electrophoresis. / QC 20101108

The aim of the thesis is the development and improvement of the experimental techniques for fluid examination. The thesis consists of two parts and both examine heat and mass transfer in liquids using the optical methods and thermal analysis. The first part deals with the measurement techniques for studying flow patterns and their stability in systems with gas/liquid interface, in particular, in a liquid bridge system. The second part is aimed at the improvement of the existing experimental techniques to study the heat/mass transfer in the mixtures with Soret effect, enclosed in a container.<p><p>Part A is motivated by preparation of the experiment JEREMI (The Japanese-European Research Experiment on Marangoni Instability) to be performed on the International Space Station (ISS). One of the objectives of the experiment is the control of the threshold of an oscillatory flow in the liquid zone by the temperature and velocity of the ambient gas. The developed set-up for a liquid bridge allows to blow gas parallel to the interface at different temperatures and investigate the effects of viscous and thermal stresses on the stability of the flow. The present study reports on isothermal experiments with moving gas and non-isothermal experiments with motionless gas when the cooling of the interface occurs due to evaporation. The discussion concerning the experimental observations is based on two sources: an interface shape measured optically and the records on thermocouples giving an indication of how temperature and frequency evolve over time.<p><p>Part B is related to ground-based studies in course of preparation and realization of the microgravity experiment DCMIX (Diffusion Coefficient in MIXtures). DCMIX project is a series of experiments aimed at measuring of the Soret coefficients in liquid mixtures on the ISS which involves a wide international group of scientists. Two experiments have been recently completed and the third one is under preparation In the course of this thesis all the aspects of the previously existing set-up for measurements of the Soret (thermal diffusion) and diffusion coefficients in binary mixtures were studied, uncertainties were identified and improvements were done to obtain reliable results. The final design has been validated by measuring coefficients in three binary benchmark mixtures and water-isopropanol. The obtained results agree well with literature data. / Doctorat en Sciences de l'ingénieur / info:eu-repo/semantics/nonPublished

La coalescence intervient dans de nombreuses situations physiques, naturelles ou industrielles, de la microphysique des nuages à la stabilité des émulsions ou l’assèchement des pétroles. Dans toutes ces situations, il est crucial de comprendre les mécanismes physiques en jeu, de manière pouvoir influencer la coalescence, la favoriser ou au contraire l’inhiber, selon les besoins. Dans cette thèse, nous étudions la coalescence dans l’air entre deux gouttes attachées et décomposons le processus global en quatre étapes : l’approche avec drainage du film d’air entre les gouttes, le perçage des interfaces, l’ouverture du pont résultant de ce perçage, les oscillations amorties conduisant à l’équilibre de la goutte résultante. Les théories décrivant les étapes 1, 2 et 4 font intervenir des modèles hydrodynamiques continus, se plaçant à une échelle macroscopique. Cependant, à l’articulation entre les deux premières étapes, intervient le perçage des interfaces, processus gouverné par des forces dont la portée correspond à une échelle de quelques dizaines de nanomètres. Une des difficultés les plus importantes dans l’étude de la coalescence est celle de l’intégration des processus ayant lieu à un niveau moléculaire, dans une théorie du continuum dont l’échelle caractéristique est bien supérieure. L’objectif est de faire le lien entre les différentes échelles : y a-t-il des interactions entre les processus se produisant à ces différentes échelles ? Pour répondre à cette question, nous développons trois axes de travail, engageant chacun une échelle caractéristique. L’un est l’étude, au niveau macroscopique du micromètre, de l’ouverture du pont liquide. Grâce à une caméra rapide, plusieurs régimes d’écoulement sont mis en évidence. Les modèles théoriques existants concernent essentiellement le régime visqueux, et aucun modèle complet ne décrit le régime purement inertiel. Nous explorons expérimentalement ce régime et décrivons la forme et la longueur du pont, à l’aide d’ondes capillaires. Nous mettons en évidence l’existence de deux lignes de très forte courbure, que nous appelons singularités, qui naissent sur le lieu de perçage des interfaces et se propagent presque sans déformation de part et d’autre. Ces singularités, conditionnées par la tension superficielle, moteur de la coalescence, façonnent la forme du pont liquide et donc l’écoulement dans ce dernier. Nous proposons un modèle simple d’écoulement inertiel, basé sur la forme du pont liée à ces singularités. Ce modèle permet de mieux comprendre les rôles des forces hydrodynamiques et de la courbure dans l’évolution temporelle de la largeur du pont. Un autre axe est une étude expérimentale par Microscope à Force Atomique, qui permet de décrire les forces responsables de la coalescence à l’échelle nanométrique, les déformations des gouttes intervenant à cette échelle et leur rôle dans la rupture des interfaces. Les mesures de forces entre goutte et flaque, puis entre deux gouttes sont effectuées avec un AFM principalement en mode dynamique de Modulation de Fréquence. Elles permettent de mettre en évidence une distance seuil de déclenchement de l’instabilité hydrodynamique responsable de la coalescence et de mesurer cette distance en fonction des propriétés physiques du liquide et du rayon des gouttes. Un diagramme de coalescence est proposé, qui permet de prévoir la valeur de la distance de déclenchement de la coalescence et le rôle des déformations d’interfaces à l’échelle nanométrique. Enfin, les oscillations du pont liquide, générées par la coalescence, sont étudiées, les modes et fréquences propres sont calculés numériquement par la méthode des éléments finis, puis comparés aux valeurs expérimentales mesurées à partir des films acquis par caméra rapide. / Coalescence is involved in numerous natural or man-made processes, from microphysics of clouds to emulsions stability, or water-crude oil separation processes. In these situations, it is crucial to understand the physics of coalescence of drops or bubbles, in order to influence the phenomenon, to enhance or inhibit the coalescence rate, depending on the needs. In this thesis, we study coalescence in air of two attached drops. We separate the coalescence process into four stages : the approach and drainage of the film between coalescing bodies, the interfaces breaking, the opening of the bridge resulting from this breaking, and the damped oscillations, generated by coalescence, leading to the equilibrium state of the resulting drop. The theoretical description of the stages 1, 2 and 4 are based on continuous hydrodynamic models, at a macroscopic scale. However, the transition between the first two stages is the interfaces break-up, controlled by short range interactions, at a nanometer scale. One of the most difficult issues is the integration of these nanoscale processes into a continuum hydrodynamic theory which length scale is much bigger. The purpose of this work is understand how the phenomenons occurring at the different scales are linked. We first study, at a macroscopic scale, the opening of the liquid bridge between the drops. Thanks to the experimental set-up, involving a high-speed camera, we explore different regimes of flow, by studying the shape and dimensions of the bridge. The existing hydrodynamic models mostly describe the viscous regime, and there exist no complete modeling of the inertial regime. We explore specifically this regime. The bridge shape is described by the mean of capillary waves. We focus on two lines of extremely high curvature on the free surface, that we call singularities, generated in the initial site of interfaces break-up, and propagating merely without deformation towards the extremities of the drops. We propose a model of inertial flow in the opening bridge, whose shape is linked to these "singularities", due to surface tension. This model allows to have a better understanding of the contribution of the hydrodynamic forces and surface tension regarding the time evolution of the length and radius of the bridge. The second area of investigation is a study at a nanometer scale. Atomic Force Microscopy (AFM) is used to measure van der Waals forces between the coalescing bodies and the nanoscale deformations leading to coalescence. We perform force measurements with an AFM, essentially in the Frequency Modulation Mode. Studying the interaction, first between a droplet and a bulk, then between two droplets, we measure the threshold distance below which the coalescence occurs, varying the physical properties of liquids and the drops radius. A coalescence diagram can be built, allowing to predict the threshold distance of coalescence and the part played by the nanoscale deformations in the process. The third point is the study of the weakly damped oscillations of the whole body, induced y coalescence. The eigen frequencies and modes are calculated using the finite elements method, and compared to the experimental results, measured by the mean of the high speed camera.